N-heterocyclomethylspiroheterocycles and fungicides containing them

ABSTRACT

N-Heterocyclomethylspiroheterocycles of the general formula I ##STR1## where A is a radical, II, III or IV ##STR2## R 2  is CH 3 , OH or OCH 3 , n is from 0 to 3, 
     R 3  is hydroxyl, acyloxy, alkoxy, unsubstituted or substituted benzoyloxy, unsubstituted or substituted benzyloxy, unsubstituted or substituted alkyl or unsubstituted or substituted alkenyl, unsubstituted or substituted aryl, 
     X is oxygen, sulfur or methylene, 
     Y is hydrogen or hydroxyl, and 
     R 1  is hydrogen, alkyl or unsubstituted or substituted cyclohexyl or unsubstituted or substituted phenyl, their addition salts with acids, and fungicides containing these compounds.

The present invention relates to N-heterocyclomethylspiroheterocycles,fungicides containing them and methods for controlling fungi using thesecompounds.

It is known that piperidinomethylspiroheterocycles, for example thecompound IX (EP 281 842), have fungicidal properties. ##STR3## However,the activity of this known compound is unsatisfactory, particularly atlow application rates and concentrations.

We have found that N-heterocyclomethylspiroheterocycles of the generalformula I ##STR4## where A is a radical II, III or IV ##STR5## R² isCH₃, OH or OCH₃, n is from 0 to 3,

R³ is hydroxyl, acyloxy, alkoxy, unsubstituted or substitutedbenzoyloxy, unsubstituted or substituted benzyloxy, unsubstituted orsubstituted alkyl or unsubstituted or substituted alkenyl, where thesubstituents are unsubstituted or substituted aryl, hydroxyl, acyloxy,alkoxy or benzyloxy, or

R³ is aryl which is unsubstituted or substituted by halogen or by alkyl,

X is oxygen, sulfur or methylene,

Y is hydrogen or hydroxyl and

R¹ is hydrogen, alkyl or unsubstituted or substituted cyclohexyl orunsubstituted or substituted phenyl, and their addition salts with acidshave an excellent fungicidal action against phytopathogenic fungi.

Particularly preferred for the purposes of the present invention areN-heterocyclomethylspiroheterocycles of the general formula I, where

A is a radical II, III or IV, as claimed in claim 1,

n is 0 or 1,

R² is CH₃, OH or OCH₃,

R³ is hydroxyl, C₁ -C₅ -acyloxy, C₁ -C₈ -alkoxy or benzoyloxy which isunsubstituted or monosubstituted to trisubstituted by halogen or C₁ -C₄-alkyl, benzyloxy which is unsubstituted or monosubstituted totrisubstituted by halogen or C₁ -C₄ -alkyl, C₁ -C₈ -alkyl which isunsubstituted or substituted by OH, aryl (phenyl), C₁ -C₅ -acyloxy,benzoyloxy, C₁ -C₈ -alkoxy or benzyloxy, or C₃ - or C₄ -alkenyl which isunsubstituted or substituted by OH, aryl (phenyl), C₁ -C₅ -acyloxy,benzoyloxy, C₁ -C₈ -alkoxy or benzyloxy, or phenyl which isunsubstituted or substituted by 1 to 3 halogen or C₁ -C₄ -alkylradicals,

X is oxygen, sulfur or methylene,

Y is hydrogen or hydroxyl,

R¹ is hydrogen, straight-chain or branched alkyl of 1 to 6 carbon atomsor phenyl which is unsubstituted or monosubstituted to trisubstituted byidentical or different alkyl radicals of 1 to 4 carbon atoms or halogenradicals, or cyclohexyl which is unsubstituted or monosubstituted totrisubstituted by identical or different C₁ -C₄ -alkyl or halogenradicals, and their addition salts with acids.

Surprisingly, the novel compounds have a better fungicidal action thanthe known compound of the formula IX, which is similar to the novelcompounds.

Formula I gives the general definition of the novel compounds.

In the formula,

A is, for example, the trans- or cis-perhydroisoquinolyl or the trans-or cis-perhydroquinolyl radical or a mixture of the correspondingcis/trans isomers or is the piperidinyl radical,

R² is methyl, hydroxyl or methoxy,

n is, for example, 0 or 1,

R³ is, for example, hydroxyl, acetoxy, benzoyloxy, C₁ -C₄ -alkoxy, suchas methoxy, ethoxy, isopropoxy or tertbutoxy, benzyloxy, C₁ -C₄ -alkyl,such as methyl, ethyl, propyl, isopropyl, sec-butyl, tert-butyl orneopentyl, phenyl, halophenyl, such as 4-fluorophenyl, C₁ -C₄-alkylphenyl, such as 4-tert-butylphenyl, hydroxymethyl, C₁ -C₄-alkoxymethyl, such as methoxymethyl, ethoxymethyl or tert-butoxymethyl,acetoxymethyl, pivaloyloxymethyl, benzyloxymethyl, benzyl, hydroxyethyl,methoxyethyl, tert-butoxyethyl, acetoxyethyl or benzoyloxyethyl,

X is, for example, oxygen, sulfur or methylene, oxygen being preferred,

Y is hydrogen or hydroxyl, hydrogen being preferred, and

R¹ is, for example, hydrogen, methyl, ethyl, 2,2-dimethylpropyl,cyclohexyl or phenyl, methyl being preferred.

Other preferred novel compounds are the adducts of acids and compoundsof the formula I in which A, n, X, Y, R¹, R² and R³ have theabovementioned meanings.

Such acids are, for example, mineral acids, such as hydrochloric acid,hydrobromic acid, phosphoric acid, sulfuric acid or nitric acid, orcarboxylic acids, such as formic acid, acetic acid, oxalic acid, malonicacid, lactic acid, malic acid, succinic acid, tartaric acid, citricacid, salicylic acid, p-toluenesulfonic acid or dodecylbenzenesulfonicacid or generally proton-acidic compounds, eg. saccharin. Salts withplant-tolerated acids are preferred (plant-tolerated salts).

The novel compounds of the formula I may be obtained in the preparationas mixtures of stereoisomers (E/Z isomers, diastereomers, enantiomers),which can be separated into the individual components in a conventionalmanner, for example by crystallization or chromatography. Both theindividual isomers and mixtures thereof can be used as fungicides andform the subject of the invention.

The novel compounds of the formula I can be prepared in a conventionalmanner (cf. EP 281 842 and 278 352) by reacting a substitutedspiroheterocycle of the general formula V ##STR6## where R¹ and X havethe abovementioned meanings and Z is an electron-attracting,nucleophilically replaceable leaving group, with a heterocycloaminederivative of the general formula VI/VII/VIII ##STR7## where R², R³, Yand n have the abovementioned meanings, in the presence or absence of adiluent and in the presence or absence of an auxiliary base.

The substituted spiroheterocycles of the general formula (V) are knownor can be prepared in a conventional manner (cf. EP 281 842 or 278 352and the literature cited therein). Some of the perhydro(iso)quinolinederivatives of the general formulae VI/VII are known; those which areunknown can be prepared by conventional processes, for example bycatalytic hydrogenation of (iso)quinoline derivatives. The piperidinederivatives of the general formula VIII are substantially known or canbe prepared by conventional processes, by hydrogenation of pyridinederivatives or derivatization of 4-hydroxypiperidines or4-hydroxyalkylpiperidines.

PREPARATION EXAMPLE 18-tert-Butyl-2-(perhydroisoquinolinomethyl)-1,4-dioxaspiro[4,5]decane(compound No. 1.1)

10 g (34 mmol) of 8-tert-butyl-2-bromomethyl-1,4-dioxaspiro[4,5]decane,5.2 g (37.4 mmol) of perhydroisoquinoline (isomer mixture) and 4.7 g (34mmol) of potassium carbonate in 100 ml of acetonitrile were refluxed for16 hours. The solvent was distilled off under reduced pressure, theresulting residue was taken up with dilute 5% strength NaOH and methyltert-butyl ether, and the organic phase was washed twice with water,dried over Na₂ SO₄ and evaporated down under reduced pressure.Fractionation of the crude product under reduced pressure gave 4.9 g ofcompound 1.1 (bp. 170° C., 0.5 mbar). Preparation of the startingcompound ##STR8##

30.15 g (120 mmol) of tin(IV) chloride were added dropwise to 115.5 g(750 mmol) of 4-tert-butylcyclohexanone in 700 ml of absolutedichloromethane at 5° C., followed by the dropwise addition of 205.5 g(1.5 mol) of epibromohydrin ##STR9## in 370 ml of absolutedichloromethane in the course of 5 hours. The mixture was stirredovernight at room temperature (20° C.), hydrolyzed with a solution of 42g of KOH in 180 ml of water while cooling, and worked up in aconventional manner. Distillation of the crude product (279 g) underreduced pressure gave 169 g (77.5%) of8-tert-butyl-2-bromomethyl-1,4-dioxaspiro[4,5]decane of boiling point110° C./0.2 mbar.

PREPARATION EXAMPLE 28-tert-Butyl-2-(4-tert-butylpiperidinomethyl)-1,4-dioxaspiro[4,5]decane(compound No.2.5)

17.4 g (123.6 mmol) of 4-tert-butylpiperidine, 9.0 g (30.9 mmol) of8-tert-butyl-2-bromomethyl-1,4-dioxaspiro[4,5]decane (cis/trans mixture)and 4.3 g (30.9 mmol) of potassium carbonate in 100 ml of absolutedimethylformamide were heated at 150° C. for 8 hours. Some of thesolvent was distilled off under reduced pressure, the residue was takenup with dilute aqueous sodium hydroxide solution/methylene chloride andthe solution was worked up in a conventional manner.

The crude product was distilled under reduced pressure to give 4.5 g ofa product of boiling point 190° C. (0.3 mbar) (diastereomer mixture).

The other novel compounds listed in Tables 1 and 2 can be prepared in asimilar manner.

                  TABLE 1                                                         ______________________________________                                         ##STR10##                     (I)                                                                                  m.p./b.p.                                                                     [°C.] IR                                                               (film)                                  No.  A                  X      R.sup.1                                                                              [cm.sup.-1 ]                            ______________________________________                                        1.1                                                                                 ##STR11##         O      CH.sub.3                                                                             170° C./ 0.5 mbar                1.2                                                                                 ##STR12##         CH.sub.2                                                                             CH.sub.3                                       1.3                                                                                 ##STR13##         O      C.sub.2 H.sub.5                                1.4                                                                                 ##STR14##         O      cyclo- hexyl                                   1.5                                                                                 ##STR15##         O      phenyl                                         1.6                                                                                 ##STR16##         O      2-methyl- propyl                               1.7                                                                                 ##STR17##         O      CH.sub.3                                       1.8                                                                                 ##STR18##         O      C.sub.2 H.sub.5                                1.9                                                                                 ##STR19##         CH.sub.2                                                                             CH.sub.3                                       1.10                                                                                ##STR20##         O      CH.sub.3                                       1.11                                                                                ##STR21##         O      C.sub.2 H.sub.5                                1.12                                                                                ##STR22##         O      CH.sub.3                                       1.13                                                                                ##STR23##         O      CH.sub.3                                       1.14                                                                                ##STR24##         O      CH.sub.3                                       1.15                                                                                ##STR25##         O      CH.sub.3                                       1.16                                                                                ##STR26##         O      CH.sub.3                                       1.17                                                                                ##STR27##         O      CH.sub.3                                       1.18                                                                                ##STR28##         O      CH.sub.3                                       1.19                                                                                ##STR29##         O      CH.sub.3                                       1.20                                                                                ##STR30##         O      CH.sub.3                                       1.21                                                                                ##STR31##         O      CH.sub.3                                       1.22                                                                                ##STR32##         O      CH.sub.3                                       1.23                                                                                ##STR33##         O      CH.sub.3                                       1.24                                                                                ##STR34##         O      CH.sub.3                                       1.25                                                                                ##STR35##         O      CH.sub.3                                       1.26                                                                                ##STR36##         O      CH.sub.3                                       1.27                                                                                ##STR37##         O      CH.sub.3                                       1.28                                                                                ##STR38##         O      CH.sub.3                                       1.29                                                                                ##STR39##         O      CH.sub.3                                       1.30                                                                                ##STR40##         O      CH.sub.3                                       1.31                                                                                ##STR41##         O      CH.sub.3                                       1.32                                                                                ##STR42##         O      CH.sub.3                                       1.33                                                                                ##STR43##         O      CH.sub.3                                       1.34                                                                                ##STR44##         O      CH.sub.3                                       1.35                                                                                ##STR45##         O      CH.sub.3                                       ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________     ##STR46##                         I                                                                     m.p., b.p. [°C.]                            No.                                                                              R.sup.1                                                                           X  R.sup.3       Y  IR (film), [cm.sup.-1 ]                            __________________________________________________________________________    2.1                                                                              CH.sub.3                                                                          O  C.sub.2 H.sub.5                                                                             H                                                     2.2                                                                              CH.sub.3                                                                          O  n-C.sub.3 H.sub.7                                                                           H                                                     2.3                                                                              CH.sub.3                                                                          O  i-C.sub.3 H.sub.7                                                                           H                                                     2.4                                                                              CH.sub.3                                                                          O  sec-C.sub.4 H.sub.9                                                                         H                                                     2.5                                                                              CH.sub.3                                                                          O  tert.-C.sub.4 H.sub.9                                                                       H  190°/0.3 mbar                               2.6                                                                              CH.sub.3                                                                          O  --C(CH.sub.3).sub.2 --CH.sub.2 --CH.sub.3                                                   H                                                     2.7                                                                              CH.sub.3                                                                          O  --C(CH.sub.3).sub.2 --CH.sub.2 --C(CH.sub.3).sub.3                                          H                                                     2.8                                                                              CH.sub.3                                                                          O  --OH          H  160°/0.15 mbar                              2.9                                                                              CH.sub.3                                                                          O                                                                                 ##STR47##    H                                                     2.10                                                                             CH.sub.3                                                                          O                                                                                 ##STR48##    H                                                     2.11                                                                             CH.sub.3                                                                          O                                                                                 ##STR49##    H                                                     2.12                                                                             CH.sub.3                                                                          O                                                                                 ##STR50##    H                                                     2.13                                                                             CH.sub.3                                                                          O  --OCH.sub.3   H                                                     2.14                                                                             CH.sub.3                                                                          O  --OC.sub.2 H.sub.5                                                                          H                                                     2.15                                                                             CH.sub.3                                                                          O  --O--CH(CH.sub.3).sub.2                                                                     H                                                     2.16                                                                             CH.sub.3                                                                          O  --O--C(CH.sub.3).sub.3                                                                      H                                                     2.17                                                                             CH.sub.3                                                                          O  --CH.sub.2 --OH                                                                             H                                                     2.18                                                                             CH.sub.3                                                                          O  --CH.sub.2 O--CH.sub.3                                                                      H                                                     2.19                                                                             CH.sub.3                                                                          O  --CH.sub.2 --O--C.sub.2 H.sub.5                                                             H                                                     2.20                                                                             CH.sub.3                                                                          O                                                                                 ##STR51##    H                                                     2.21                                                                             CH.sub.3                                                                          O  --CH.sub.2 --CH.sub.2 --OH                                                                  H                                                     2.22                                                                             CH.sub.3                                                                          O                                                                                 ##STR52##    H                                                     2.23                                                                             CH.sub.3                                                                          O  C.sub.6 H.sub.5                                                                             H                                                     2.24                                                                             CH.sub.3                                                                          O  C.sub.6 H.sub.5                                                                             OH 200°/0.1 mbar                               2.25                                                                             CH.sub.3                                                                          O  4-F--C.sub.6 H.sub.5                                                                        OH                                                    2.26                                                                             CH.sub.3                                                                          O  C.sub.6 H.sub.5 --CH.sub.2 --                                                               H  oil                                                2.27                                                                             CH.sub.3                                                                          O  C.sub.6 H.sub.5 (CH.sub.2).sub.2 --                                                         H                                                     2.28                                                                             CH.sub.3                                                                          O  C.sub.6 H.sub.5 (CH.sub.2).sub.3 --                                                         H  oil; 2939,1465,1323,                                                          1195,1103 cm.sup.-1                                2.29                                                                             CH.sub.3                                                                          O  4-t-C.sub.4 H.sub.9 --C.sub.6 H.sub.4 --                                                    H                                                     2.30                                                                             CH.sub.3                                                                          S  i-C.sub.3 H.sub.7                                                                           H                                                     2.31                                                                             CH.sub.3                                                                          S  tert.-C.sub.4 H.sub.9                                                                       H                                                     2.32                                                                             CH.sub.3                                                                          S  C(CH.sub.3).sub.2 --CH.sub.2 CH.sub.3                                                       H                                                     2.33                                                                             CH.sub.3                                                                          S  OH            H                                                     2.34                                                                             CH.sub.3                                                                          S  O--CH.sub.3   H                                                     2.35                                                                             CH.sub.3                                                                          S  O--C.sub.2 H.sub.5                                                                          H                                                     2.36                                                                             CH.sub.3                                                                          S                                                                                 ##STR53##    H                                                     2.37                                                                             CH.sub.3                                                                          S                                                                                 ##STR54##    H                                                     2.38                                                                             CH.sub.3                                                                          S  C.sub.6 H.sub.5                                                                             H                                                     2.39                                                                             CH.sub.3                                                                          S  C.sub.6 H.sub.5                                                                             OH                                                    2.40                                                                             CH.sub.3                                                                          CH.sub.2                                                                         i-C.sub.3 H.sub.7                                                                           H                                                     2.41                                                                             CH.sub.3                                                                          CH.sub.2                                                                         sec-C.sub.4 H.sub.9                                                                         H                                                     2.42                                                                             CH.sub.3                                                                          CH.sub.2                                                                         tert.-C.sub.4 H.sub.9                                                                       H                                                     2.43                                                                             CH.sub.3                                                                          CH.sub.2                                                                         C(CH.sub.3).sub.2 --CH.sub.2 CH.sub.3                                                       H                                                     2.44                                                                             CH.sub.3                                                                          CH.sub.2                                                                         C(CH.sub.3).sub.2 --CH.sub.2 --C(CH.sub.3).sub.3                                            H                                                     2.45                                                                             CH.sub.3                                                                          CH.sub.2                                                                         OH            H                                                     2.46                                                                             CH.sub.3                                                                          CH.sub.2                                                                         O--CH.sub.3   H                                                     2.47                                                                             CH.sub.3                                                                          CH.sub.2                                                                         O--C.sub.2 H.sub.5                                                                          H                                                     2.48                                                                             CH.sub.3                                                                          CH.sub.2                                                                          ##STR55##    H                                                     2.49                                                                             CH.sub.3                                                                          CH.sub.2                                                                          ##STR56##    H                                                     2.50                                                                             CH.sub.3                                                                          CH.sub.2                                                                         CH.sub.2 --OH H                                                     2.51                                                                             CH.sub.3                                                                          CH.sub.2                                                                         CH.sub.2 --OCH.sub.3                                                                        H                                                     2.52                                                                             CH.sub.3                                                                          CH.sub.2                                                                         CH.sub.2 --O--C.sub.2 H.sub.5                                                               H                                                     2.53                                                                             CH.sub.3                                                                          CH.sub.2                                                                          ##STR57##    H                                                     2.54                                                                             CH.sub.3                                                                          CH.sub.2                                                                         CH.sub.2 CH.sub.2 OH                                                                        H                                                     2.55                                                                             CH.sub.3                                                                          CH.sub.2                                                                         CH.sub.2 CH.sub.2 --OCH.sub.3                                                               H                                                     2.56                                                                             CH.sub.3                                                                          CH.sub.2                                                                          ##STR58##    H                                                     2.57                                                                             CH.sub.3                                                                          CH.sub.2                                                                         C.sub.6 H.sub.5                                                                             H                                                     2.58                                                                             CH.sub.3                                                                          CH.sub.2                                                                         C.sub.6 H.sub.5                                                                             OH                                                    2.59                                                                             CH.sub.3                                                                          CH.sub.2                                                                         C.sub.6 H.sub.5 --CH.sub.2                                                                  H                                                     2.60                                                                             CH.sub.3                                                                          CH.sub.2                                                                         C.sub.6 H.sub.5 --(CH.sub.2).sub.3 --                                                       H                                                     2.61                                                                             CH.sub.3                                                                          CH.sub.2                                                                         4-tert.-C.sub.4 H.sub.9 --C.sub.6 H.sub.4                                                   H                                                     2.62                                                                             H   O  C.sub.2 H.sub.5                                                                             H                                                     2.63                                                                             H   O  i-C.sub.3 H.sub.7                                                                           H                                                     2.64                                                                             H   O  t-C.sub.4 H.sub.9                                                                           H                                                     2.65                                                                             H   O  --OH          H                                                     2.66                                                                             H   O  --O--CH.sub.3 H                                                     2.67                                                                             H   O                                                                                 ##STR59##    H                                                     2.68                                                                             H   O  C.sub.6 H.sub.5                                                                             H                                                     2.69                                                                             H   O  C.sub.6 H.sub.5                                                                             OH                                                    2.70                                                                             H   O  C.sub.6 H.sub.5 CH.sub.2                                                                    H                                                     2.71                                                                             C.sub.2 H.sub.5                                                                   O  C.sub.2 H.sub.5                                                                             H                                                     2.72                                                                             C.sub.2 H.sub.5                                                                   O  n-C.sub.3 H.sub.7                                                                           H                                                     2.73                                                                             C.sub.2 H.sub.5                                                                   O  i-C.sub.3 H.sub.7                                                                           H                                                     2.74                                                                             C.sub.2 H.sub.5                                                                   O  sec-C.sub.4 H.sub.9                                                                         H                                                     2.75                                                                             C.sub.2 H.sub.5                                                                   O  tert.-C.sub.4 H.sub.9                                                                       H                                                     2.76                                                                             C.sub.2 H.sub.5                                                                   O  --C(CH.sub.3).sub.2 --CH.sub.2 --CH.sub.3                                                   H                                                     2.77                                                                             C.sub.2 H.sub.5                                                                   O  --C(CH.sub.3).sub.2 --CH.sub.2 --C(CH.sub.3).sub.3                                          H                                                     2.78                                                                             C.sub.2 H.sub.5                                                                   O  --OH          H                                                     2.79                                                                             C.sub.2 H.sub.5                                                                   O                                                                                 ##STR60##    H                                                     2.80                                                                             C.sub.2 H.sub.5                                                                   O                                                                                 ##STR61##    H                                                     2.81                                                                             C.sub.2 H.sub.5                                                                   O                                                                                 ##STR62##    H                                                     2.82                                                                             C.sub.2 H.sub.5                                                                   O                                                                                 ##STR63##    H                                                     2.83                                                                             C.sub.2 H.sub.5                                                                   O  --OCH.sub.3   H                                                     2.84                                                                             C.sub.2 H.sub.5                                                                   O  --OC.sub.2 H.sub.5                                                                          H                                                     2.85                                                                             C.sub.2 H.sub.5                                                                   O  --O--C(CH.sub.3).sub.3                                                                      H                                                     2.86                                                                             C.sub.2 H.sub.5                                                                   O  --CH.sub.2 --OH                                                                             H                                                     2.87                                                                             C.sub.2 H.sub.5                                                                   O  --CH.sub.2 --O--CH.sub.3                                                                    H                                                     2.88                                                                             C.sub.2 H.sub. 5                                                                  O  --CH.sub.2 --OC.sub.2 H.sub.5                                                               H                                                     2.89                                                                             C.sub.2 H.sub.5                                                                   O                                                                                 ##STR64##    H                                                     2.90                                                                             C.sub.2 H.sub.5                                                                   O  --CH.sub.2 --CH.sub.2 --OH                                                                  H                                                     2.91                                                                             C.sub.2 H.sub.5                                                                   O                                                                                 ##STR65##    H                                                     2.92                                                                             C.sub.2 H.sub.5                                                                   O  C.sub.6 H.sub.5                                                                             H                                                     2.93                                                                             C.sub.2 H.sub.5                                                                   O  4-tert.-C.sub.4 H.sub.9 --C.sub.6 H.sub.4                                                   H                                                     2.94                                                                             cyclo-                                                                            O  tert.-C.sub.4 H.sub.9                                                                       H                                                        hexyl                                                                      2.95                                                                             C.sub.6 H.sub.5                                                                   O  tert.-C.sub.4 H.sub.9                                                                       H                                                     __________________________________________________________________________

Generally speaking, the novel compounds are extremely effective on abroad spectrum of phytopathogenic fungi, in particular those from theAscomycetes and Basidiomycetes classes. Some of them have a systemicaction and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in vegetables and fruit.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi. Either the fungi themselves, or the plants,seeds, materials or soil to be protected against fungal attack aretreated with a fungicidally effective amount of the active ingredient.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient. The application rates arefrom 0.02 to 3 kg or more of active ingredient per hectare, depending onthe type of effect desired. The novel compounds may also be used forprotecting materials (wood), for example against Paecilomyces variotii.

When the active ingredients are used for treating seed, amounts of from0.001 to 50, and preferably from 0.01 to 10, g per kg of seed areusually employed.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 1.1 is mixed with 10 parts byweight of N-methyl-α-pyrrolidone. A mixture is obtained which issuitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 2.5 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound no. 1.1 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water andfinely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 2.5 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into water and uniformlydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 1.1 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 2.5 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 1.1 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 40 parts by weight of compound no. 2.5 is intimately mixed with 10parts by weight of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater to give a stable aqueous dispersion. Dilution in water gives anaqueous dispersion.

IX. 20 parts by weight of compound no. 1 is intimately mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in an increase in thefungicidal spectrum.

USE EXAMPLES

The compound8-tert-butyl-2-(piperidino-N-methyl)-1,4-dioxaspiro[4.5]-decane (A)disclosed in EP 281,842 was used for comparison purposes.

USE EXAMPLE 1 Action on wheat brown rust

Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dustedwith spores of brown rust (Puccinia recondita). The pots were thenplaced for 24 hours at 20° to 22° C. in a high-humidity (90-95%)chamber. During this period the spores germinated and the germ tubespenetrated the leaf tissue. The infected plants were then sprayed torunoff with aqueous liquors containing (dry basis) 80% of activeingredient and 20% of emulsifier. After the sprayed-on layer had dried,the plants were set up in the greenhouse at 20° to 22° C. and a relativehumidity of 65 to 70%. The extent of rust fungus spread on the leaveswas assessed after 8 days.

The results show that active ingredients nos. 1.1 and 2.5, applied as0.006 wt % spray liquors, had a better fungicidal action (100%) thanprior art comparative agent A (75%).

USE EXAMPLE 2 Action on cucumber mildew

Leaves of pot-grown cucumber seedlings of the "Chinesische Schlange"variety were sprayed at the two-leaf stage with a spore suspension ofcucumber mildew. After about 20 hours, the plants were sprayed to runoffwith aqueous liquors containing (dry basis) 80% of active ingredient and20% of emulsifier. After the sprayed-on layer had dried, the plants wereset up in the greenhouse at 20°-22° C. and a relative humidity of70-80%. The extent of fungus spread was determined after 21 days.

The results show that active ingredients nos. 1.1 and 2.5, applied as0.025% spray liquors, had a better fungicidal action (100%) than priorart comparative agent A (40%).

We claim:
 1. A compound of the formula ##STR66## or an acid additionsalt thereof, wherein R³ is hydroxyl, C₁ -C₅ -alkanoyloxy, C₁ -C₈-alkoxy, benzoyloxy which is unsubstituted or mono- to trisubstituted byhalogen or C₁ -C₄ -alkyl, benzyloxy which is unsubstituted or mono- totrisubstituted by halogen or C₁ -C₄ -alkyl, t-butyl C₅ -C₈ -alkyl, C₁-C₈ -alkyl which is substituted by phenyl, C₁ -C₅ -alkanoyloxy,benzoyloxy, C₁ -C₈ -alkoxy or benzyloxy, or C₃ -C₄ -alkenyl which isunsubstituted or substituted by OH, phenyl, C₁ -C₅ -alkanoyloxy,benzoyloxy, C₁ -C₈ -alkoxy or benzyloxy, or phenyl which isunsubstituted or substituted by 1 to 3 halogen or C₁ -C₄ -alkylradicals,X is oxygen, Y is hydrogen or hydroxyl, R¹ is hydrogen,straight-chain or branched alkyl of 1 to 6 carbon atoms, phenyl which isunsubstituted or mono- to trisubstituted by identical or different alkylradicals of 1 to 4 carbon atoms or halogen atoms, or cyclohexyl which isunsubstituted or mono- to trisubstituted by identical or different C₁-C₄ -alkyl or halogen atoms.
 2. A compound according to claim 1 whereinR¹ is methyl or ethyl and R³ is tert-butyl, phenyl, benzyl, orphenylpropyl. 3.8-(2-Methylbut-2-yl)-2-[(4-tert-butylpiperidino)methyl]-1,4-dioxaspiro[4,5]decane.4.8-tert-Butyl-2-(4-tert-butylpiperidinomethyl)-1,4-dioxaspiro[4,5]decane.